Azaborolidine compounds

ABSTRACT

The new azaborolidine compounds of the formula: WHEREIN R1 and R2 represent alkyl of one through four carbon atoms, or R1 and R2 together with the nitrogen atom collectively represent a mononuclear 5- or 6-membered heterocyclic group, X represents hydrogen, halogen, alkyl, alkoxy or alkylthio of one through four carbon atoms, or trifluoromethyl or dimethylsulphamoyl, and at least one of the carbon atoms of the trimethylene chain linking the nitrogen and boron atoms can be substituted by alkyl of one through four carbon atoms, possess fungicidal, insecticidal acaricidal and herbicidal properties.

United States Patent Comettiet al.

[54] AZABOROLIDINE COMPOUNDS [72] inventors: Andrew Cometti,Maisons-Alfort; Jean Fouche, Bourg-la-Reine; Yves Le Goff,Bretigny-sur-Orge, all of France [73] Assignee: Rhone-Poulenc S.A.,Paris, France [22] Filed: Feb. 2, 1970 [2]] Appl. No.: 8,034

[30] Foreign Application Priority Data 6 Feb. 3, 1969 France ..6902292[52] US. Cl. ..260/268 R, 260/247, 260/247.l, 260/247.7, 260/293.65,260/326.84,

260/326.85, 260/551 B, 260/556 AR,

[51] Int. Cl. ..C07d 107/02 [58] Field of Search...260/556, 551, 268,293, 293.4, 260/294.7, 247, 247.1, 247.7, 326.5, 326.8,

[56] References Cited UNITED STATES PATENTS 3,201,464 8/1965 Brown etal. ..260/551 [4 1 Oct. 3, 1972 Primary Examiner-Henry R. JilesAssistant Examiner-Harry l. Moatz Attorney-Stevens, Davis, Miller &Mosher [57] ABSTRACT The new azaborolidine compounds of the formula:

16 Claims, No Drawings AZABOROLIDINE COMPOUNDS This invention relates tonew boron derivatives, to a process for their preparation, andcompositions containing them.

The new boron derivatives of the present invention are those of thegeneral formula:

wherein R and R represent alkyl radicals containing one to four carbonatoms, which may be the same or different, or R and R together with thenitrogen atom to which they are attached collectively represent amononuclear 5- or 6- membered heterocyclic group, which may contain asecond hetero atom selected from nitrogen, oxygen and sulphur, such asl-pyrrolidinyl, piperidino, morpholino or a 4-alkyl-l-piperazinyl group,X represents a hydrogen or halogen atom, an alkyl, alkoxy or alkylthioradical containing one to four carbon atoms, or a trifluoromethyl ordimethylsulphamoyl radical, and one or more of the carbon atoms of thetrimethylene chain linking the nitrogen and boron atoms in theazaborolidine ring can be substituted by at least one alkyl radicalcontaining one to four carbon atoms, e.g. the chain can be CH CH(Cl-l)Cl-l,.

According to a feature of the invention, the boron derivatives ofgeneral formula I are prepared by reaction of a diphenylboron compoundof the general formula:

wherein R, and R are as hereinbefore defined, Hal represents a halogenatom, and one or more of the carbon atoms of the trimethylene chain canbe substituted by at least one alkyl radical containing one to fourcarbon atoms.

III

When Y in general formula II represents a 2- aminoethoxy orZ-dimethylaminoethoxy radical the reactant can be written in the cyclicform:

wherein R and R are the same and represent hydrogen atoms or methylradicals.

The reaction is carried out in an inert organic solvent, for examplediethyl ether or tetrahydrofuran, at a temperature between 0 C. and theboiling point of the reaction mixture, and is followed by hydrolysis ofthe organometal reaction product using conditions known per se, e.g.with aqueous ammonium chloride or hydrochloric acid. The boronderivatives of general formula I thus obtained can optionally bepurified by physical methods such as crystallization or chromatography.

The starting materials of general formula ll wherein Y represents ahalogen atom can be obtained, for example, according to the methodindicated by .l. Soulie and P. Cadiot, Bull. Soc. Chim., p. 1981 (1966).The starting materials of general formula II wherein Y represents aZ-aminoethoxy or 2-dimethylaminoethoxy radical [i.e. the1,3,2-oxazaborolidine compounds of general formula IV] or an alkoxyradical can be obtained, for example, according to the methods describedby Y. Rasiel and BK. Zimmerman Jr., Ann. 649, Ill (1961) or by R.L.Letsinger and I. Skoog, J. Am. Chem. Soc., 77, 2491 (1955).

The new boron derivatives of general formula I possess interestingfungicidal, insecticidal, acaricidal and herbicidal properties.

The fungicidal activity is polyvalent and is shown against beananthracnose (Colletrotrichum lindemuthianum), tomato mildew(Phytophthora infestans), tobacco mildew (Peronospora tabaci), cucumbermildew (Erysiphe cichoracearum) and wheat rust (Puccinia glumarum) atquantities of between 10 and 200 g. of active substance per hectoliterof liquid diluent such as water.

The insecticidal activity -is shown, more particularly by contact,against diptera (Musca domestica), coleoptera (Tribolium confusum) andlepidaptera (caterpillars such as Plutella maculipennis) at quantitiesof between 10 and g. of active substance per hectoliter of liquiddiluent.

The acaricidal activity, which is combined with good persistence, is ofvalue against phytophagic acarids (Tetranychus telarius) at quantitiesof between 10 and 100 g. of active substance per hectoliter of liquiddiluent. At quantities of between 50 and 200 g. of active substance perhectoliter, a considerable ovicidal activity is exhibited.

The herbicidal activity is shown more particularly by pre-emergenceapplication against gramineal (foxtail) at quantities of between 0.5 and5 kg. of active substance per hectare.

Preferred boron derivatives of general formula I are those wherein Xrepresents a hydrogen or halogen (e. g. chlorine or fluorine) atom, oran alkyl (e.g. methyl or butyl), alkoxy (e.g. methoxy) or alkylthio(e.g. methylthio) radical; more particularly those wherein R and Rrepresent methyl radicals, or R and R together with the nitrogen atom towhich they are attached represent a 4-alkyl-l-piperazinyl group, andespecially those such compounds wherein both symbols X represent thesame atom or group.

The present invention also includes within its scope fungicidal,insecticidal, acaricidal and herbicidal compositions which contain, asthe active ingredient, at least one boron derivative of general formulaI in association with one or more diluents or adjuvants compatible withthe boron compound(s) and suitable for use in agriculture. Preferablythe compositions contain between 50 and 0.005 percent by weight of boroncompound.

The compositions may be solid if there is employed a powdered solidcompatible diluent such as talc, calcined magnesia, kieselguhr,tricalcium phosphate, powdered cork, absorbent charcoal, or a clay suchas kaolin or bentonite. These solid compositions are preferably preparedby grinding the boron compound with the solid diluent, or byimpregnating the solid diluent with a solution of the boron compound ina volatile solvent, evaporating the solvent, and if necessary grindingthe product so as to obtain a powder.

Instead of a solid diluent, there may also be used a liquid in which theboron compound is dissolved or dispersed. The compositions may thus takethe form of suspensions, emulsions or solutions in organic oraqueous-organic media, for example acetophenone, aromatic hydrocarbonssuch as toluene or xylene, or mineral, animal or vegetable oils, ormixtures of these diluents. The compositions in the form of suspensions,emulsions or solutions may contain wetting, dispersing or emulsifyingagents of the ionic or non-ionic type, for example sulphoricinoleates,quaternary ammonium derivatives or products based on ethylene oxidecondensates, such as condensates of ethylene oxide with octylphenol, orfatty acid esters of anhydrosorbitols which have been rendered solubleby etherification of the free hydroxyl radicals by condensation withethylene oxide. It is preferable to use agents of the nonionic typebecause they are not sensitive to electrolytes. When emulsions arerequired, the boron compounds may be used in the form ofself-emulsifying concentrates containing the active substance dissolvedin the emulsifying agent or in a solvent containing an emulsifying agentcompatible with the boron compound and solvent, a simple addition ofwater to such concentrates producing compositions ready for use.

These compositions, which can be solid or liquid, optionally containother fungicides, insecticides, acaricides and/or herbicides compatiblewith the boron compounds of general formula 1. By way of example,suitable insecticides are phosphorus-containing derivatives such asparathion or phosalone; suitable fungicides are organic compounds suchas maneb or benomyl; suitable herbicides are triazines such as simazine,ureas such as monurone, or phenoxyacetic acid derivatives such as2,4-dichlorophenoxyacetic acid.

The new boron derivatives of general formula I are preferably employedas pesticides or herbicides in a quantity of 50 to g. of activesubstance per hectoliter of water and generally, depending on thespecies of pest or weed, the type of infestation and the degree ofinfestation, an amount of between 500 and 3000 liters of such aqueouscompositions per hectare is necessary.

The following Examples illustrate the invention.

EXAMPLE 1 A solution of diphenylchloroborane (29 g.) in anhydrousdiethyl ether (30 cc.) is added over a period of 15 minutes to asolution of Grignard reagent prepared from magnesium (3.96 g.) and1-chloro-3- dimethylaminopropane (20 g.) in tetrahydrofuran (35 cc.) at25 C. The reaction mixture is refluxed for 1 hour and, after evaporationof the solvents under reduced pressure 20 mm.l-lg), the residue isdissolved in chloroform (200 cc.) and then treated with a 30 percent(w/v) aqueous solution of ammonium chloride cc.). The chloroform layeris decanted and the aqueous phase is extracted twice with chloroform(total 100 cc.). The chloroform solution is washed twice with water(total 100 cc.), dried over anhydrous sodium sulphate and thenevaporated under reduced pressure (20 mm.l-lg). Recrystallization of theresulting crude product from ethanol (700 cc.) yields 1,1-dimethyl-2,2-diphenyl-l,2-azaborolidine (20 g.) melting at 156 C.

Diphenylchloroborane employed as starting material can be preparedaccording to J. Soulie and P. Cadiot, Bull. Soc. Chim. p. 1981 (1966).

EXAMPLE 2 A solution of butyl diphenylborinate (10.8 g.) intetrahydrofuran (10 cc.) is added over a period of 10 minutes to asolution of a Grignard reagent prepared from magnesium (1.55 g.) and1-chloro-3- dimethylaminopropane (7.8 g.) in tetrahydrofuran (30 cc.) at30 C. The reaction mixture is left for one hour at 20 C. and is thenhydrolysed with a 30 percent (w/v) aqueous solution of ammonium chloride(40 cc.).

After evaporation of the tetrahydrofuran under reduced pressure (20mm.l-lg), the product is extracted four times with benzene (total 400cc.). The benzene solutions are combined, washed three times withdistilled water (total 150 cc.) and dried over anhydrous sodiumsulphate. The residual oil is crystallized from ethanol (20 cc.) to givel,l-dimethyl-2,2-diphenyl-l ,2- azaborolidine 1.22 g.) melting at 156 C.

Butyl diphenylborinate employed as starting material can be preparedaccording to the method of R.L. Letsinger and l. Skoog, J. Am. Chem.Soc., 77, 2491 (1955).

EXAMPLE 3 A solution of 2,2-diphenyl-3,3-dimethyl-1,3,2-oxazaborolidine(8.4 g.) in tetrahydrofuran (80 cc.) is added over a period of 13minutes to a solution of a Grignard reagent prepared from magnesium(2.64 g.) and l-chloro-3dimethylaminopropane (12.1 g.) intetrahydrofuran (30 cc.) at 30 C. The reaction mixture is refluxed for 1hour and, after evaporation of the solvent under reduced pressuremmJ-lg). the residue is dissolved in chloroform (100 cc.) and is thenhydrolysed with a 30 percent (w/v) aqueous solution of ammonium chloride(100 cc.). The chloroform layer is decanted and the aqueous phase isextracted twice with chloroform (total 150 cc.). The combined chloroformsolutions are dried over anhydrous sodium sulphate and then evaporatedunder reduced pressure (20 mm.Hg). The residue is crystallized fromethanol (20 cc.) to give 1,1-dimethyl-2,2-diphenyl-l,2- azaborolidine(2.6 g.) melting at 156 C.

2 ,2-Diphenyl-3 ,3-dimethyl-l ,3 ,2-oxazaborolidine employed as startingmaterial can be prepared according to H. Weidmann and H.K. Zimmerman,Ann., 619, 28 (1958).

EXAMPLE 4 A solution of diphenylchloroborane (17 g.) in anhydrousdiethyl'ether (30 cc.) is added over a period of 10 minutes to asolution of a Grignard reagent prepared from magnesium (2.64 g.) andl-ch1oro-3- dimethylamino-2-methylpropane (13.5 g.) in tetrahydrofuran(30 cc.) at C. The reaction mixture is refluxed for 1 hour and, afterevaporation of the solvents under reduced pressure (20 mm.l-lg), theresidue is dissolved in chloroform (200 cc.) and then hydrolysed with apercent (w/v) aqueous solution of ammonium chloride (100 cc.). Thechloroform layer is decanted and the aqueous phase is extracted twicewith chloroform (total 100 cc.). The chloroform solution is washed threetimes with distilled water (total 150 cc.), dried over anhydrous sodiumsulphate and then evaporated under reduced pressure (20 mm.l-lg). Afterrecrystallization of the resulting crude product from acetonitrile (150cc.), l,1,4-trimethyl-2,Z-diphenyl-l,2 -azaborolidine (15.3 g.), meltingat 165 C., is obtained.

EXAMPLE 5 A solution of diphenylchloroborane (22.5 g.) in anhydrousdiethyl ether cc.) is added over a period of 13 minutes to a solution ofa Grignard reagent prepared from magnesium (3.3 g.) and1-(3-chloropropyl)-4- methylpiperazine (20 g.) in tetrahydrofuran cc.)at 60 C. The reaction mixture is left for 4 hours 30 minutes at atemperature of about 20 C. The residue obtained after concentration ofthe reaction mixture under reduced pressure (20 mm.Hg) is dissolved inchloroform (200 cc.) and then treated with a 30 percent (w/v) aqueoussolution of ammonium chloride (200 cc.). The chloroform layer isdecanted, washed twice with water (total 100 cc.), dried over anhydroussodium sulphate and then concentrated under reduced pressure (20mm.l-lg). The resulting oil (30.7 g.) is taken up in N hydrochloric acid(250 cc.) and extracted three times with diethyl ether (total 100 cc.).The aqueous phase is rendered alkaline by addition of 5N sodiumhydroxide solution until a pH of 10 is reached, and is then extractedthree times with benzene (100 cc.) and dried over anhydrous sodiumsulphate. After concentration under reduced pressure (20 mmHg), theresidue is solidified by trituration in diisopropyl ether (50 cc.).Recrystallization from isopropanol (225 cc.) yields1,1-diphenyl-8-methyl-lboro-S-azonia-8-azaspiro[4,5ldecane (6.3 g.)melting at 176 C.

EXAMPLE 6 Bis(4-fluorophenyl)chloroborane (23.6 g.) dissolved inanhydrous diethyl ether (30 cc.) is added over a period of 22 minutes toa solution of a Grignard reagent prepared from magnesium (3.65 g.) andl-chloro-3- dimethylaminopropane (18.2 g.) in tetrahydrofuran (30 cc.).The reaction mixture is refluxed for 5 hours and is then kept for 16hours at a temperature of about 20 C. The residue obtained afterconcentration under reduced pressure (20 mm.l-lg) is dissolved inchloroform (200 cc.). The solution thus obtained is treated with a 30percent (w/v) aqueous solution of ammonium chloride (1 10 cc.). Thechloroform layer is decanted, washed twice with water (total 100 cc.)and dried over anhydrous sodium sulphate. After concentration underreduced pressure (20 mm.Hg) and recrystallization of the residue fromethanol (35 cc.), 1 1 -dimethyl-2,2-bis(4-fluorophenyl 1 ,2-azaborolidine (18.5 g.), melting at 1 18 C., is obtained.

Bis(4-fluorophenyl)chloroborane employed as starting material can beprepared as follows:

Butyl bis(4-fluorophenyl)borinate (47 g.) and phosphorus pentachloride(35.7 g.) are heated at 100 C. until a solution is obtained. Afterevaporation of the volatile products under reduced pressure (20 mm.l-lg)at C., the residual oil is distilled under reduced pressure to givebis(4-fluorophenyl)chloroborane (39 g.) distilling at 108 C./0.4 mm.Hg.

Butyl bis(4-fluorophenyl) borinate can be prepared by esterifyingbis(4-fluoropheny1)borinic acid (71 g.) with butanol (400 cc.), thereaction being carried out in toluene (1 liter) and the water formedbeing removed by azeotropic distillation. Distillation under reducedpressure yields butyl bis(4-fluorophenyl)borinate (85 g.), b.p. 138C./0.4 mm.l-lg.

Bis(4-fluorophenyl)borinic acid can be prepared by hydrochloric acidhydrolysis of its aminoethyl ester, which can be prepared according toUS. Pat. No. 3,117,854.

EXAMPLE 7 cc.) and dried over anhydrous sodium sulphate.

The residue obtained after concentration of the solvents under reducedpressure (20 mm.l-lg) is recrystallized from propanol (250 cc.) to givel,l-dimethyl-2,2- bis( 3-chlorophenyl)-l ,2-azaborolidine (14.3 g.)melting at 121 C.

Bis(3-chlorophenyl)chloroborane employed as starting material can beprepared as follows:

Butyl bis( 3-chlorophenyl)borinate (71 g.) and phosphorus pentachloride(50 g.) are heated at 100 C. with stirring until a solution is obtained.After concentration of the solution under reduced pressure (20 mm.Hg) at90 C., the residual oil is distilled to givebis(3-ch1orophenyl)chloroborane (46.5 g.), b.p. 173-179 C./0.1 mm.l-1g.

Butyl bis(3-chlorophenyl)borinate can be prepared by esterification ofbis(3-chlorophenyl)boronic acid (68 g.) with butanol (288 cc.), thereaction being carried out in toluene (1140 cc.) and the water formedbeing removed by azeotropic distillation. Distillation under reducedpressure yields butyl bis(3-chlorophenyl)borinate (71 g.), b.p. 167C./0.4 mm.l-lg.

Bis(3-ch1oropheny1)borinic acid can be prepared by hydrochloric acidhydrolysis of its aminoethyl ester or 2,2-bis(3-chlorophenyl)-1,3,2-oxazaboro1idine (m.p. 142 C.) which can be prepared according to themethod of Y. Rasiel and 1-1.K. Zimmerman Jr., Ann., 649,111 (1961).

EXAMPLE 8 Bis( 4-chlorophenyl)chloroborane (22 g.) dissolved inanhydrous diethyl ether (50 cc.) is added over a period of 16 minutes,while cooling by means of a water bath, to a solution of a Grignardreagent prepared from magnesium (2.5 g.) and 1-chloro-3-dimethylaminopropane (12.4 g.) in tetrahydrofuran (30 cc.). After 16hours at a temperature of about 20 C., the solvents are evaporated underreduced pressure (20 mm.l-1g) and the resulting residue is dissolved inchloroform (200 cc.). The chloroform solution is treated with a 30percent (w/v) aqueous solution of ammonium chloride (100 cc.), decanted,washed three times with water (total 150 cc.) and then dried overanhydrous sodium sulphate. After concentration by removal of thesolvents under reduced pressure (20 mm.1-1g), the resulting residue issuccessively recrystallized from isopropanol (75 cc.) and then fromethanol (50 cc.) to give 1,1-dimethyl-2,2-bis-(4-chlorophenyl)-1,2-azaborolidine g.) melting at 107 C.

Bis(4-chlorophenyl)chloroborane (47 g.) employed as starting material(b.p. 160-170 C./0.5 mm.l-lg) can be prepared by reaction of phosphoruspentachloride (53 g.) with butyl bis(4 chlorophenyl)borinate (78 g.).

Butyl bis(4-chlorophenyl)borinate (b.p. 170 C./0.2 mm.Hg) can beprepared according to the method described by Hawthorne, .I. Am. Chem.Soc., 80, 4295 1958).

EXAMPLE 9 A solution of 3-dimethylaminopropylmagnesium chloride intetrahydrofuran (100 cc.: 1.46 mole/liter) is added over a period of 40minutes to a solution of butyl bis(4-ch1orophenyl)borinate (50 g.) intetrahydrofuran (270 cc.) at 20 C. After 16 hours at a temperature ofabout 20 C., the solvents are evaporated under reduced pressure (20mm.Hg) and the resulting residue is dissolved in chloroform (300 cc.).The chloroform solution is then hydrolysed with hydrochloric acid 163cc.) and the organic phase is decanted, washed with water (150 cc.) anddried over anhydrous sodium sulphate. After evaporation of thechloroform under reduced pressure 20 mm.l-lg), the resulting residue isrecrystallized from ethanol (65 cc.) to give 1,1-dimethyl-2,2-bis(4-chlorophenyl)-1,2-azaborolidine (32 g.) melting at107 C.

EXAMPLE 10 A solution of 3-dimethylaminopropylmagnesium chloride intetrahydrofuran (49 cc.: 1.74 mole/liter) is added over a period of 8minutes to a suspension of 2,2-bis-(4-methoxyphenyl)-1,3,2-oxazaborolidine (6.9 g.) in anhydrousdiethyl ether (40 cc.) at 15 C. The reaction mixture is then heatedunder reflux for 16 hours. The resulting yellow solution is hydrolysedwith a 20 percent (w/v) aqueous solution of ammonium chloride 40 cc.).The organic layer is separated by decantation and washed twice withwater (total 30 cc.) and dried over anhydrous sodium sulphate. Theresidue obtained after concentration under reduced pressure (20 mm.l-lg)is recrystallized from isopropanol (15 cc.) to give 1, l-dimethy1-2,2-bis(4-methoxyphenyl )-1 ,2- azaborolidine (5.3 g.) meltingat 107 C.

2,2-Bis(4-methoxyphenyl)-1,3,2-oxazaborolidine (m.p. 185 C.) employed asstarting material can be prepared according to the method described byY. Rasiel and BK. Zimmerman Jr., Ann., 649, 1 1 1 (1961).

EXAMPLE 1 1 A solution of a Grignard reagent prepared from magnesium(7.2 g.) and 1-ch1oro-3-dimethy1aminopropane (36.2 g.) intetrahydrofuran cc.) is added over a period of 20 minutes to asuspension of 2,2-bis(4- methylthiophenyl)-1,3,2-oxazaborolidine (30 g.)in anhydrous diethyl ether (50 cc.). The reaction mixture is heatedunder reflux for 16 hours. The yellow solution obtained is hydrolysedwith a 20 percent (w/v) aqueous solution of ammonium chloride cc.). Theorganic layer is decanted, washed four times with water (total 200 cc.)and dried over anhydrous sodium sulphate. After concentration underreduced pressure (20 mm.l-lg), the residue obtained is solidified bytrituration in acetonitrile (20 cc.) and is then twice recrystallizedfrom acetonitrile (25 cc.) and then from ethanol (75 cc.).1,1-Dimethyl-2,2-bis(4-methylthiophenyl)- 1,2-azaborolidine (4.5 g.),melting at 103 C., is thus obtained.

2,2-Bis(4-methylthiopheny1)-1,3,2-oxazaborolidine (m.p. l92195 C.)employed as starting material can be prepared according to the methoddescribed by Y. Rasiel and H.K. Zimmerman Jr., Ann, 649, 1 l 1 1961).

EXAMPLE 12 A solution of a Grignard reagent prepared from magnesium (11.6 g.) and 1-chloro-3- dimethylaminopropane (45 g.) in tetrahydrofuran(200 cc.) is added to a suspension of2,2-bis(4-methylphenyl)-l,3,2-oxazaborolidine (27.8 g.) in anhydrousdiethyl ether (200 cc.). The reaction mixture is heated under reflux for16 hours. After cooling, the resulting solution is hydrolysed with a 10percent (w/v) aqueous solution of ammonium chloride (200 cc.). Theorganic layer is decanted, washed four times with water (250 cc.) andthen dried over anhydrous sodium sulphate. After concentration underreduced pressure (20 mmHg), the resulting residue is solidified bytriturating in methanol (25 cc.). After recrystallization from hexane(30 cc.), 1,1-dimethy1-2,2-bis(4-methylphenyl)- l,2-azaborolidine (9.4g.), melting at 106 C., is obtained.

2,2-Bis(4-methylphenyl )-1 ,3,2-oxazaborolidine (m.p. 205 C.) employedas starting material can be prepared according to'Y. Rasiel andH.K..Zimmerman Jr.,Ann.,649, 111 (1961).

EXAMPLE 13 A solution of 3-dimethylaminopropylmagnesium chloride intetrahydrofuran (55 Co: 1.58 mole/liter) is added over a period of 35minutes to a solution of butyl bis(4-methylphenyl)borinate (23 g.) intetrahydrofuran (125 cc.) at l C. The reaction mixture is maintained atthat temperature for 1 hour and then at about 25 C. for 16 hours. Afterconcentration under reduced pressure (20 mm.Hg), the residue obtained istaken up in chloroform (200 cc.) and hydrolysed with N hydrochloric acid(43 cc.). After decantation, the organic layer is washed twice withwater (200 cc.) and then dried over anhydrous sodium sulphate. Afterconcentration under reduced pressure (20 mm.Hg), the resulting crudeproduct is recrystallized from isopropanol cc.) to givel,l-dimethyl-2,2-bis(4- methylphenyl)-l ,2-azaborolidine (7.8 g.)melting at 106 C.

Butyl bis(4-methylphenyl)borinate (b.p. 160 C./0.2 mm.Hg) employed asstarting material can be obtained according to Hawthorne, J. Am. Chem.Soc., 80, 4295 (1958).

EXAMPLE 14 A solution of 3-dimethylaminopropylmagnesium chloride intetrahydrofuran (28.8 00.: 1.58 mole/liter) is added over a period of 15minutes to a solution of 3,3-dimethyl-2,2-bis(4-methylphenyl)-1,3,2-oxazaborolidine (12.7 g.) intetrahydrofuran (125 cc.) at 25 C. After 16 hours at about25 C., thetetrahydrofuran is evaporated under reduced pressure (20 mm.Hg). Theresulting residue is taken up in chloroform (125 cc.) and hydrolysedwith a 20vpercent (w/v) aqueous solution of ammonium chloride (12.2cc.). After decantation, the chloroform layer is washed six times withwater (100 cc.) and then dried over anhydrous sodium sulphate. Theresidue obtained after concentration under reduced pressure (20 mm.Hg)is recrystallized from isopropanol (10 cc.) to give l,l-dimethyl-2,2-bis(4-methylphenyl)-l ,2azaborolidine (6.7 g.) melting at 106 C.

3,3-Dimethyl-2,2-bis(4-methylphenyl)-1,3,2-oxazaborolidine (m.p. 136 C.)can be prepared according to the method of Y. Rasiel and H.l(. ZimmermanJr.,Ann.649,ll1 (1961).

EXAMPLE 15 A solution of 3-dimethylaminopropylmagnesium chloride intetrahydrofuran (33.3 cc.: 1.7-9 mole/liter) at is added to a solutionof bis(2-chlorophenyl)chloroborane (16 g.) in tetrahydrofuran (50 cc.)at 45 C. After 16 hours at a temperature of about 20 C., the solution isconcentrated under reduced pressure (20 mm.Hg). The residue obtained isdissolved in chloroform (100 cc.) and the resulting solution ishydrolysed with a 30 percent (w/v) aqueous solution of ammonium chloride(70 cc.). After decantation, the organic phase is washed twice withwater (total 100 cc.) and is then dried over anhydrous sodium sulphate.The residue obtained after concentration under reduced pressure (20mm.Hg) 'is recrystallized from ethanol (20 cc.) to givel,l-dimethyl-2,2-bis(2- chloropheny1)-1,2-azaborolidine (5 g.) meltingat 139 C EXAMPLE 16 A solution of 3-dibutylaminopropylmagnesium chloridein tetrahydrofuran (49 cc.: 0.8 mole/liter) is added to a solution ofbis(4-methylphenyl)chloroborane (9 g.) in tetrahydrofuran cc.). After 16hours at a temperature of about 20 C., the tetrahydrofuran is evaporatedunder reduced pressure (20 mm.Hg). The residue obtained is taken up inchloroform (100 cc.) and the solution is then hydrolysed with a 10percent (w/v) aqueous solution of ammonium chloride (100 cc.). Afterdecantation, the organic layer is washed three times with water (150cc.) and then dried over anhydrous sodium sulphate. The residue obtainedafter concentration under reduced pressure (20 mm.Hg) is solidified bytrituration in methanol (15 cc.). After filtration and thenrecrystallization from methanol cc.)., 1,1-dibutyl-2,2-bis(4-methylphenyl)-l,2-azaborolidine (2.2 g.), melting at about84C., is obtained.

Bis(4-methylphenyl)chloroborane (b.p. C./O.1 mm.Hg) employed as startingmaterial can be prepared according to RI. Paetzold, P.P. Habederer andR. Muellbauer, J. Organometal. Chem., 7, 45-90 1967).

EXAMPLE 17 A condensation product of octylphenol and ethylene oxidecontaining 10 moles of ethylene oxide per mole of octylphenol (10 partsby weight) is added to a solution of 1 l-dimethyl-2,2-bis(4-chlorophenyl)-1 ,2- azaborolidine (25 parts byweight) in a mixture of equal parts (by volume) of toluene andacetophenone (65 parts by volume). The resulting solution is used, afterdilution with water, in the ratio of 200 cc. of this solution per 100liters of water.

EXAMPLE 18 A condensation product of octylphenol and ethylene oxidecontaining 10 moles of ethylene oxide per mole of octylphenol (10 partsby weight) is added to a solution ofl,l-dimethyl-2,2-bis(4-methylphenyl)-1,2- azaborolidine (25 parts byweight) in a mixture of equal parts (by volume) of toluene andacetophenone (65 parts by volume). The resulting solution is used, afterdilution with water, in the ratio of 200 cc. of this solution per 100liters of water.

EXAMPLE 19 A condensation product of octylphenol and ethylene oxidecontaining 10 moles of ethylene oxide per mole of octylphenol (10 partsby weight) is added to a solution of l,l-dimethyl-2,2-diphenyl-1,2-azaborolidine (25 parts by weight) in amixture of equal parts (by volume) of toluene and acetophenone (65 partsby volume). The resulting solution is used, after dilution with water,in the ratio of 200 cc. of this solution per 100 liters of water.

We claim: 1. An azaborolidine of the formula: 0025 wherein R and R eachrepresent alkyl of one through four carbon atoms, or R and R togetherwith the nitrogen atom to which they are attached collectively representl-pyrrolidinyl, piperidino, morpholino or 4-alkyl-l-piperazinyl with onethrough four carbon atoms in the alkyl radical, X represents hydrogen,halogen, alkyl, alkoxy or alkylthio of one through four carbon atoms,trifluoromethyl or dimethylsulphamoyl, and at least one of the carbonatoms of the trimethylene chain linking the nitrogen and boron atoms inthe azaborolidine ring can be substituted by alkyl of one through fourcarbon atoms.

2. An azaborolidine according to claim 1 wherein X represents hydrogen,halogen, or alkyl, alkoxy or alkylthio of one through four carbon atoms.

3. An azaborolidine according to claim 1 wherein both symbols Xrepresent the same atom or group.

4. The azaborolidine according to claim 1 which is l,1-dimethyl-2,2-dipheny1-l ,2-azaborolidine.

5. The azaborolidine according to claim 1 which is l,1-dimethyl-2,2-bis(4-fluorophenyl)-l ,2- azaborolidine.

6. The azaborolidine according to claim 1 which is 1,1-dimethyl-2,2-bis(3-chlorophenyl)-l ,2- azaborolidine.

7. The azaborolidine according to claim 1 which is 1,l-dimethyl-2,2-bis(4-chlorophenyl)-1,2- azaborolidine.

8. The azaborolidine according to claim 1 which is l l-dimethyl-2,2-bis(4-methoxyphenyl l ,2- azaborolidine.

9. The azaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(4-methylthiophenyl)-l ,2- azaborolidine.

10. The azaborolidine according to claim 1 which is l l-dimethyl-2,2-bis(4-methylphenyl)-l ,2- azaborolidine.

11. The azaborolidine according to claim 1 which is 1,1-dimethyl-2,2-bis(2-chl0rophenyl)-l ,2- azaborolidine.

12. The azaborolidine according to claim 1 which is 1 ,1,4-trimethyl-2,2-diphenyl-1,2-azaborolidine.

13. The azaborolidine according to claim 1 which is l,l-dibutyl-2,2-bis( 4-methylphenyl)-l ,2- azaborolidine.

14. The azaborolidine according to claim 1 which is l, l-diphenyl-8-methyll -boro-5-azonia-8-azaspiro-[ 4,5 decane.

1 An azaborolidine according to claim 1 wherein R and R each representalkyl of one through four carbon atoms.

16. An azabrolidine according to claim 1 wherein R and R representmethyl.

2. An azaborolidine according to claim 1 wherein X represents hydrogen,halogen, or alkyl, alkoxy or alkylthio of one through four carbon atoms.3. An azaborolidine according to claim 1 wherein both symbols Xrepresent the same atom or group.
 4. The azaborolidine according toclaim 1 which is 1,1-dimethyl-2,2-diphenyl-1,2-azaborolidine.
 5. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(4-fluorophenyl)-1,2-azaborolidine.
 6. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(3-chlorophenyl)-1,2-azaborolidine.
 7. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(4-chlorophenyl)-1,2-azaborolidine.
 8. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(4-methoxyphenyl)-1,2-azaborolidine.
 9. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(4-methylthiophenyl)-1,2-azaborolidine.
 10. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(4-methylphenyl)-1,2-azaborolidine.
 11. Theazaborolidine according to claim 1 which is1,1-dimethyl-2,2-bis(2-chlorophenyl)-1,2-azaborolidine.
 12. Theazaborolidine according to claim 1 which is1,1,4-trimethyl-2,2-diphenyl-1,2-azaborolidine.
 13. The azaborolidineaccording to claim 1 which is1,1-dibutyl-2,2-bis(4-methylphenyl)-1,2-azaborolidine.
 14. Theazaborolidine according to claim 1 which is1,1-diphenyl-8-methyl-1-boro-5-azonia-8-azaspiro-(4,5)decane.
 15. Anazaborolidine according to claim 1 wherein R1 and R2 each representalkyl of one through four carbon atoms.
 16. An azabrolidine according toclaim 1 wherein R1 and R2 represent methyl.